CN102414764B - Substrate for superconducting wiring, superconducting wiring and production method for same - Google Patents
Substrate for superconducting wiring, superconducting wiring and production method for same Download PDFInfo
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- CN102414764B CN102414764B CN201080018860.8A CN201080018860A CN102414764B CN 102414764 B CN102414764 B CN 102414764B CN 201080018860 A CN201080018860 A CN 201080018860A CN 102414764 B CN102414764 B CN 102414764B
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- 239000000758 substrate Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 239000011651 chromium Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 59
- 239000002184 metal Substances 0.000 abstract description 59
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 64
- 239000000463 material Substances 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- 229910000856 hastalloy Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000151 deposition Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 239000002887 superconductor Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- ZLHLYESIHSHXGM-UHFFFAOYSA-N 4,6-dimethyl-1h-imidazo[1,2-a]purin-9-one Chemical compound N=1C(C)=CN(C2=O)C=1N(C)C1=C2NC=N1 ZLHLYESIHSHXGM-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910003470 tongbaite Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed is a low-cost metal substrate which is resistant to high temperature oxidation, has excellent strength, is non-magnetic and is ideal for use for high-temperature superconducting wiring used at liquid nitrogen temperature. Austenitic stainless steel containing at least 0.4% by weight of nitrogen is used as a metal substrate for superconducting wiring. After 700-950 DEG C heat treatment in the high-temperature super conducting layer formation step is carried out, the metal substrate has an extremely high 0.2% proof stress at liquid nitrogen temperature.
Description
Technical field
The present invention relates to the metal substrate of the superconducting wire using for the superconduction instrument such as hyperconductive cable and superconducting magnet.
Background technology
Up to now, RE base super conductor (RE: rare earth element) has been acknowledged as a kind of high-temperature superconductor that demonstrates superconductivity at liquid nitrogen temperature (77K) or higher temperature.Especially, by chemical formula YBa
2cu
3o
7-ythe yttrium base super conductor (after this, it is called as Y base super conductor or YBCO) representing is representational superconductor.
Conventionally, utilize the superconducting wire of RE base super conductor (after this, it is called as RE base superconducting wire) there is stacked structure, wherein, on strip metal substrate, stacking in order layer (after this, it is called as RE base superconducting layer) and the stabilizing layer that has intermediate layer, made by RE base super conductor.
In RE base superconducting wire, RE base Superconducting Crystals need to be arranged to (biaxial orientation) one-tenth seems monocrystal.Therefore, propose: utilize the orientation metal substrate of the recrystallization texture that uses this type of fcc metal with face-centered cube (fcc) structure as the method for superconducting layer being carried out to the template of biaxial orientation; And the method pressure orientation intermediate layer of mandatory biaxial orientation being deposited by ion beam assisted depositing (IBAD) method etc.
In these two kinds of methods, be necessary, metal substrate can be processed the thickness into about 0.1mm.In a kind of front method, because needs metal substrate is biaxially oriented itself, so Ni sill, Ag sill, Cu sill or their composite material are used as the raw material of metal substrate.Meanwhile, in a kind of rear method, do not impose on metal substrate about the restriction of orientation etc., and substantially can use any metal substrate, as long as this metal substrate can bear this stacking of intermediate layer and superconducting layer.
By way of parenthesis, for RE base superconducting wire is used for applying instrument, for the substrate for RE base superconducting wire, require following condition:
(1) the RE base superconducting wire being formed by substrate should have high strength;
(2), under serviceability temperature, substrate should be nonmagnetic; And
(3), under the formation condition of intermediate layer and superconducting layer, substrate should have enough corrosion resistances.
In the method in intermediate layer that uses pressure orientation, often Hastelloy C276 alloy (Hastelloy is registered trade mark) non magnetic and that have excellent high-temperature oxidation resistance (corrosion resistance) and intensity is used as to metal substrate (for example, patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open communique No.2001-266666
Patent documentation 2: Japanese Patent Laid-Open communique No.H11-302798
Patent documentation 3: Japanese Patent Laid-Open communique No.H08-269632
summary of the invention
The problem to be solved in the present invention
But, due to Hastelloy C276 alloy use the element that a large amount of prices are higher (as, Ni and W), so Hastelloy C276 alloy be very expensive (price higher than
10,000/kg), and this is to hinder the principal element that RE base superconducting wire price reduces.
Thus, need nonmagnetic and there is the cheap metal substrate of the high-temperature oxidation resistance equal with Hastelloy C276 and intensity.
What note is, austenitic stainless steel is known be nonmagnetic, there is excellent corrosion resistance and can obtain high-intensity metal material, be still not clear (for example,, with reference to patent documentation 2 and 3) but whether relevant austenitic stainless steel meets for the desired above-mentioned characteristic of substrate of superconducting wire.
In order to address the above problem, make the present invention.An object of the present invention is to provide a kind of cheap metal substrate, it is suitable as the material of the hts tape using in liquid nitrogen temperature or lower than the temperature of liquid nitrogen temperature, and it is nonmagnetic and has excellent high-temperature oxidation resistance and intensity.
The method of dealing with problems
On the one hand, the invention provides a kind of substrate for the hts tape that uses in liquid nitrogen temperature or lower than the temperature of liquid nitrogen temperature,
Wherein, described substrate by contain percentage by weight be 0.4% or the austenitic stainless steel of higher nitrogen make.
In an embodiment of the substrate of this superconducting wire, it is 20% or higher chromium that described austenitic stainless steel contains percentage by weight.
In an embodiment of the substrate of this superconducting wire, it is 0.05% or lower carbon that described austenitic stainless steel contains percentage by weight.
In an embodiment of the substrate of this superconducting wire, described austenitic stainless steel contain percentage by weight be 5% or higher manganese and percentage by weight be 10% or lower nickel.
On the other hand, the invention provides a kind of superconducting wire, it forms superconducting layer across intermediate layer on substrate, described substrate by comprise percentage by weight be 0.4% or the austenitic stainless steel of higher nitrogen make.
In an embodiment of this superconducting wire, it is 20% or higher chromium that described austenitic stainless steel contains percentage by weight.
In an embodiment of this superconducting wire, it is 0.05% or lower carbon that described austenitic stainless steel contains percentage by weight.
In an embodiment of this superconducting wire, described austenitic stainless steel contain percentage by weight be 5% or higher manganese and percentage by weight be 10% or lower nickel.
In an embodiment of this superconducting wire, described substrate is 1200MPa or higher in 0.2% yield stress of liquid nitrogen temperature.
Again on the one hand, the invention provides a kind of manufacture method of superconducting wire, the method comprises the following steps:
By contain percentage by weight be 0.4% or higher nitrogen and percentage by weight be 0.05% or the substrate made of the austenitic stainless steel of lower carbon on form intermediate layer; And
On described intermediate layer, form superconducting layer,
Wherein, in forming the step in described intermediate layer and forming one of step of described superconducting layer, carry out the heat treatment of 700 ℃ to 950 ℃.
Be well known that, as disclosed in patent documentation 2 and 3, N (nitrogen) is for improving the intensity of superconduction substrate at normal temperature.But, in patent documentation 2 or 3, even if clearly do not describe after the material relevant with superconducting wire is exposed to high temperature in superconducting wire manufacture process, also keep the intensity of low temperature.Conventionally, when in the time that high temperature is annealed to metal, discharge its dislocation, and further, occur its recrystallization.Accordingly, unless in metal, react to generate compound, metal is softened, to reduce the intensity of superconducting wire.
Inventor of the present invention has concentrated on attentiveness more cheap than Hastelloy C276 and has been on nonmagnetic austenitic stainless steel.Inventor carries out rechecking, by making the composition element optimization of austenitic stainless steel, makes austenitic stainless steel can be applied to the substrate for superconducting wire.Then, inventor finds, by adjusting the N content in austenitic stainless steel, to have improved the intensity of austenitic stainless steel at low temperature with experiment.And inventor confirms: even austenitic stainless steel stands high-temperature heat treatment in the step that forms superconducting layer, also kept the intensity of expecting.In addition, inventor has been found that: by adjusting the content of Ni (nickel), C (carbon), Mn (manganese) and Cr (chromium) in austenitic stainless steel, can prevent because the Ni diffusion from metal substrate reduces superconducting characteristic, and can realize the corrosion resistance of expectation.
As mentioned above, completed the present invention based on doing painstaking research of inventor of the present invention, and by adjusting the content of N in austenitic stainless steel, the present invention makes austenitic stainless steel can be applied to the substrate of superconducting wire.
Invention effect
According to the present invention, a kind of cheap metal substrate is provided, it is suitable for use as the material of superconducting wire, and it is nonmagnetic and has excellent high-temperature oxidation resistance and intensity.So by using this metal substrate to manufacture superconducting wire, the price that can realize thus superconducting wire reduces.
Accompanying drawing explanation
Fig. 1 shows according to the figure of the stacked structure of the superconducting wire of an execution mode.
Fig. 2 shows according to the table that becomes to be grouped into of the metal substrate of an example and comparative example.
Fig. 3 shows according to the table of the characteristic evaluation result of the metal substrate of this example and these comparative example.
Fig. 4 shows the figure of relation between annealing temperature and substrate intensity (0.2% yield stress).
Fig. 5 shows and becomes to be grouped into and the table of characteristic evaluation result according to the metal substrate of this example and these comparative example.
Embodiment
Describe an embodiment of the invention below in detail.
Fig. 1 shows according to the figure of the stacked structure of the superconducting wire of this execution mode.
As shown in Figure 1, RE base superconducting wire 1 has stacked structure, wherein, forms in order intermediate layer 12, superconducting layer 13 and stabilizing layer 14 on strip metal substrate 11.
In this embodiment, metal substrate 11 be made by non magnetic austenitic stainless steel without orientation metal substrate.Intermediate layer 12 is for example, by comprising biaxial orientation layer (, the GZO, (Gd for the crystal of superconducting layer 13 being orientated along fixed-direction
2zr
2o
7)) and form.For example form this biaxial orientation layer by IBAD method.
In this embodiment, metal substrate 11 has following composition.In other words, metal substrate 11 is made by having the austenitic stainless steel that following one-tenth is grouped into:
N: percentage by weight is 0.4% or higher;
Ni: percentage by weight is 10% or lower;
C: percentage by weight is 0.05% or lower;
Mn: percentage by weight is 5% or higher;
Cr: percentage by weight is 20% or higher; And
Fe and inevitably impurity, as residue.
And metal substrate 11 can comprise Al, Si, the Mo etc. as the composition element of general austenitic stainless steel.
N is interstitial atom, and has strengthened intensity and the corrosion resistance of metal substrate 11.In the time that the content of N in metal substrate is less than 0.4% (percentage by weight), can not realize intensity and the corrosion resistance expected.Accordingly, the content of N is set to 0.4% (percentage by weight) or higher.Note, in the time that the content of N is greater than 1.5% (percentage by weight), is difficult to be suppressed to the pore while point solidifying, and is difficult to composition to be processed as substrate.Therefore, the content of expectation N is set to 1.5% (percentage by weight) or lower.
Like this, metal substrate 11 becomes and has the intensity desired at low temperature, particularly, becomes at low temperature and has the intensity equal or higher with the intensity of Hastelloy C276.Therefore, metal substrate 11 is suitable for use as the substrate at the superconducting wire of liquid nitrogen temperature (77K) or lower temperature use.And, in the manufacture process of superconducting wire 1, deposit superconducting wire 13 by mocvd method, superconducting wire 1 is heated to 800 ℃ nearly; But, even under these circumstances, also kept the intensity in the time of low temperature.
In addition,, by the high fact of the intensity of metal substrate 11, can prevent from after deposition intermediate layer 12 and superconducting layer 13, occurring the defect as peeled off, and can improve the critical current properties of superconducting wire 1.
In the time that the content of Ni in metal substrate 11 is greater than 10% (percentage by weight), increase the possibility that may arrive superconducting layer 13 from the Ni diffusion of metal substrate 11.Therefore, expect that it is 10% or lower that the content of Ni is set to percentage by weight.
Like this, can reduce the Ni diffusion from metal substrate 11.Accordingly, can alleviate because the fact of Ni diffusion arrival superconducting layer 13 has reduced superconducting characteristic.Note, Ni is for stable austenite phase and improve its machinability, and the content of expecting Ni to be set to percentage by weight be 7% or higher, to utilize this effect.
In the time that the content of C in metal substrate 11 is greater than 0.05% (percentage by weight), tend to for example, generate at high temperature (, 700 ℃ to 950 ℃, as the heat treatment temperature in the formation step of superconducting layer 13) carbide of Cr.Therefore, expect that it is 0.05% or lower that the content of C is set to percentage by weight.
Like this, can be suppressed at the carbide of high temperature generation Cr.Accordingly, can prevent the corrosion resistance that reduces to reduce superconducting wire 1 due to solid solution Cr amount.Note, although C is generally used for improving intensity, C is easy to reduce the toughness of superconducting wire in liquid nitrogen temperature (as its serviceability temperature) or lower temperature.Accordingly, less C addition is preferred.
In the time that the content of Mn in metal substrate 11 is less than 5% (percentage by weight), the DeGrain of the solid solution capacity of stable austenite phase and raising N.Accordingly, the content of expectation Mn is set to 5% (percentage by weight) or higher.Meanwhile, in the time that the content of Mn is greater than 10% (percentage by weight), reduced the hot-workability of substrate, and this makes to be difficult to relevant substrate is processed.Therefore, more preferably, the content of Mn is set to 10% (percentage by weight) or lower.And, in the time that the content of Mn increases, even if the content of Ni has reduced that amount, also can stable austenite phase.Therefore, owing to can reducing the content of Ni, so can more effectively reduce Ni diffusion.
In the time that the content of Cr in metal substrate 11 is less than 20% (percentage by weight), cannot realize the corrosion resistance of expectation.Therefore, expect that it is 20% or higher that the content of Cr is set to percentage by weight.
Like this, can improve the corrosion resistance of superconducting wire 1.Note, in austenitic stainless steel, to be preferably set to percentage by weight be 30% or lower to the content of Cr, and more preferably, percentage by weight is 25%.Its reason is as follows.Be 30% or when higher when the content of Cr becomes percentage by weight, Cr solid solution completely, and become the nitride of Cr, and this has not only reduced the N adding and also makes thus corrosion resistance, fatigue strength, toughness and ductility deteriorated, and obvious deteriorated hot-workability further.
What note is, in the temperature range of 650 ℃ to 950 ℃, be significant by the carbon Chromium Carbide Formation in steel, and it is said by being heated to 1100 ℃ to 1200 ℃ or higher temperature, chromium carbide decomposes and solid solution again, although this temperature is according to composition and difference.In superconducting wire 1, its temperature becomes 700 ℃ nearly in the time of deposition intermediate layer 12, and becomes 850 ℃ nearly in the time of deposition superconducting layer 13.Accordingly, superconducting wire 1 remains in the generation temperature of chromium carbide.
Therefore, in the time there is a large amount of carbon in metal substrate 11, generate a large amount of chromium carbides, thus, should form the Cr deficiency of passivating film, and not form strong passivating film.Therefore, the abnormal oxidation that occurs due to nickel etc. can not be suppressed on the surface of metal substrate 11, and the diffusion from metal substrate 11 to superconducting layer 13 such as nickel can not be suppressed.
Meanwhile, carbon amount in metal substrate 11 is little, unlikely Chromium Carbide Formation forms by Cr on the surface of metal substrate 11
2o
3deng the strong passivating film of making.Therefore, in both situations of situation that deposit intermediate layer 12 and superconducting layer 13, even if the oxygen providing passes intermediate layer 12 grades and is diffused on the surface of metal substrate 11, also can suppress the lip-deep Quick Oxidation of metal substrate 11 by passivating film in the time of deposition.In addition, can also suppress the diffusion from metal substrate 11 to superconducting layer 13 such as nickel by passivating film.
[example]
In example, there is the stainless steel of the composition shown in Fig. 2 (percentage by weight) as baseplate material.That is to say, baseplate material is to have the austenitic stainless steel that following one-tenth is grouped into: C: percentage by weight is 0.02%; Mn: percentage by weight is 6%; Ni: percentage by weight is 10%; Cr: percentage by weight is 23%; Mo: percentage by weight is 2%; N: percentage by weight is 0.5% and as the Fe of residue and inevitable impurity.
This austenitic stainless steel suitably stands intermediate annealing, and is rolled into the thickness of 0.1mm.Then, the austenitic stainless steel rolling is like this cut open, and to be formed as thus having the section of 10mm width, and each section is as metal substrate 11.
This metal substrate 11 stands surface grinding, and thereafter, at normal temperature, GZO layer (biaxial orientation layer) is deposited on to the thickness to 1 μ m on this metal substrate by IBAD method.And, on GZO layer, under the heating-up temperature of 700 ℃, by sputtering method by CeO
2layer (cap rock) is deposited into the thickness of 500nm.That is to say, in example, intermediate layer 12 is by GZO layer and CeO
2layer composition.
Then,, on intermediate layer 12, the heating-up temperature of 850 ℃, by mocvd method, Y base superconducting layer 13 is deposited into the thickness of 1 μ m.And, on Y base superconducting layer 13, suitably deposit Ag protective layer, and in oxygen flow, make Ag protective layer stand oxygen annealing at 550 ℃.
[comparative example]
In comparative example 1 to 3, as the material of each substrate, use SUS304 (general austenitic stainless steel, 18Cr-8Ni-0.06C), SUS316LN (18Cr-12Ni-2Mo-N-0.02C) and Hastelloy C276, and to manufacture superconducting wire with mode like example class.Note, the composition of each baseplate material is shown in Figure 2, and these steel grade class titles are the addresses in JIS.
For the superconducting wire of manufacturing in example 1 and comparative example 1 to 3, in liquid nitrogen, by 4 terminal methods, under the voltage definition of 1 μ V/cm, measure critical current.And, for superconducting wire, carry out tensile test in room temperature and liquid nitrogen temperature (77K), and measure 0.2% yield stress.Note, as for 0.2% yield stress of superconducting wire, after deposition superconducting layer 13, peel off intermediate layer 12 and superconducting wire 13, only carry out tensile test for metal substrate 11, and measure 0.2% yield stress.As for high-temperature oxidation resistance (corrosion resistance), after stacking intermediate layer 12 and superconducting layer 13, carry out the observation of peeling off in superconducting layer 13, and determine high-temperature oxidation resistance based on whether occurring peeling off.
Assessment result has been shown in Fig. 3.Fig. 3 also shows the intensity (in 0.2% yield stress of room temperature) of metal substrate monomer, for reference.
As shown in Figure 3, according to the superconducting wire of example have with according to the equal critical current properties of the superconducting wire of comparative example 3 (its use Hastelloy C276 as substrate).And according in the superconducting wire of example, its 0.2% yield stress in room temperature is according to the approximately 70-80% of 0.2% yield stress of the superconducting wire of comparative example 3; But its 0.2% yield stress at 77K demonstrates higher than according to the value of 0.2% yield stress of the superconducting wire of comparative example 3.Think and occurred putting forward high-intensity effect by N (nitrogen).In each example in example and comparative example 3, it is good observing by peeling off after deposition superconducting layer the high-temperature oxidation resistance obtaining.
And, aspect critical current properties and high-temperature oxidation resistance, be better than using austenitic stainless steel in the identical Price Range comparative example 1 and 2 as substrate according to the superconducting wire of example, and aspect intensity, be also greatly better than comparative example 1 and 2.
And, in order to confirm the intensity of substrate self, carry out annealing for the Hastelloy C276 using in the baseplate material using in example and comparative example 3, and thereafter, carry out tensile test in room temperature and liquid nitrogen temperature (77K).Note, annealing time is set to 30 minutes.
Test result has been shown in Fig. 4.As shown in Figure 4, be that after quilt is rolled, the intensity of the baseplate material using in example and Hastelloy C276 is equal to substantially each other at baseplate material and Hastelloy C276.In the time improving annealing temperature, at room temperature, the intensity of the strength ratio Hastelloy C276 of the baseplate material in example is low; But, the baseplate material in example in the intensity of the low temperature to 77K (as serviceability temperature) on the contrary higher than the intensity of Hastelloy C276.Particularly, according in the baseplate material of example, stand the heat treatment of 700 ℃ to 950 ℃ at relevant baseplate material after, baseplate material becomes 1200MPa or higher in 0.2% yield stress of liquid nitrogen temperature.
Like this, be understood that, in the environment for use (in this environment for use, metal substrate is used at low temperature after high annealing) of the special like this metal substrate for superconducting wire, the baseplate material using in example is better than Hastelloy C276 aspect intensity.
When consider the price of the baseplate material using in example be Hastelloy C276 price 1/6 time, it is very effective should understanding that relevant baseplate material reduces for the price that realizes superconducting wire.As mentioned above, according to the baseplate material using in example 1, although can realize cheapness corrosion resistance excellent and there is the superconducting wire of high critical current.
With with mode like above-mentioned example class, there is the each stainless steel section of the composition shown in Fig. 5 (percentage by weight) as baseplate material, and like execution and above-mentioned example class, characteristic evaluation and machinability are assessed.Note, about machinability assessment, how to change and determine machinability in the time being processed to the thickness of 0.1mmt based on basic material.In the case of such sample can without any defect process, sample is assessed as " two circle " mark.In the case of such sample can there is no defect and processes, this sample is assessed as " individual pen " mark.Can be processed at such sample but occur disconnecting and wait and exist a lot of defects, this sample is assessed as " triangle " mark.Can not be processed to 0.1mmt at such sample, this sample is assessed as " fork-shaped " mark.
In each sample of sample 1 to 10, a kind of composition of structure, the percentage by weight that makes the nitrogen content in austenitic stainless steel can be 0 to 1.5%.
Result from Fig. 5, is appreciated that in the situation that nitrogen content is less than 0.4% (percentage by weight), corrosion resistance than the percentage by weight of nitrogen content be 0.4% or higher situation end poor.Meanwhile, in the case of the percentage by weight of nitrogen content be 0.4% or higher to 1.5% or lower, each such sample has the corrosion resistance of expectation, and this is preferred.And, in the situation that nitrogen content is greater than or equal to 0.5% (percentage by weight) and is less than or equal to 1.0% (percentage by weight), should understand the critical current (Ic) in the superconducting wire that can obtain desired value or higher value conduct use substrate, and this is preferred.
Note, in the situation that nitrogen content is greater than 1.5% (percentage by weight), be difficult to baseplate material to be processed into substrate; But, for example, by utilizing Solid Solution Nitriding method can form the austenitic stainless steel that contains high concentration N.Solid Solution Nitriding method is so a kind of chemical heat treatment method: to keep steel and nitrogen-atoms to diffuse to thus the mode of solid phase (austenite phase) from material surface in 1000 ℃ or higher high temperature nitrogen, near the nitrogen of realizing material surface or in whole material increases.
In each sample of sample 4 and 11 to 17, a kind of composition of structure, the percentage by weight that makes the chromium content in austenitic stainless steel can be 10% to 40%.
Should be appreciated that at the percentage by weight of chromium content and be less than (sample 11 and 12) 20%, corrosion resistance than the percentage by weight of chromium content be 20% or higher situation ( sample 4 and 13 to 17) slightly poor.Meanwhile, should be understood that at the percentage by weight of chromium content and be greater than (sample 15 to 17) 30%, machinability than the percentage by weight of chromium content be 30% or lower situation ( sample 4 and 11 to 14) poor.
Therefore, the percentage by weight of chromium content be 20% or higher to 30% or lower situation be most preferred.
In each sample in sample 4 and 18 to 23, a kind of composition of structure, the percentage by weight that makes the carbon content in austenitic stainless steel can be 0.02% to 0.5%.
Learn following: in the case of the percentage by weight of carbon content be 0.05% or lower ( sample 14,17 and 18), each sample has the corrosion resistance of expectation, and has higher critical current (Ic) value; But, exceeding (sample 19 to 23) 0.05% at the percentage by weight of carbon content, its corrosion resistance is poor, and critical current (Ic) is also lower than the critical current in sample 4,17 and 18.Occur that owing to identifying many pick-up points in superconducting layer, therefore thinking this situation is because reduced critical current (Ic) by peeling off.
It is believed that, owing to reacting each other by heat the Cr and the C that make in substrate in the time depositing superconducting layer, to generate as Cr
23c
6sediment, reduced in substrate effectively Cr element, and as Cr
2o
3the formation of passivating film become insufficient, so cause the selective oxidation forming by Ni in substrate etc., therefore occur that this peels off.
Therefore, preferably, the percentage by weight of the carbon content in austenitic stainless steel is 0.05% or lower.
In each sample in sample 4,24 and 25, a kind of composition of structure, the percentage by weight that makes the nickel content in austenitic stainless steel can be 5% to 15%.
With the percentage by weight of nickel content be 10% or lower situation (sample 4 and 24) compare, be that in 15% situation (sample 25), corrosion resistance is slightly poor, and critical current (Ic) is also low at the percentage by weight of nickel content.Its reason is considered to: because the nickel concentration containing in austenitic stainless steel is high, so produce the nickel diffusion that reaches superconducting layer.
Therefore, preferably, the percentage by weight of the nickel content in austenitic stainless steel is 10% or lower.
In sample 4 and 26 to 28 each, a kind of composition of structure, the percentage by weight that makes the content of manganese in austenitic stainless steel can be 6% to 15%.
Compare with the situation (sample 4 and 27) that the percentage by weight of manganese content is 5% to 10%, be less than in the sample 26 of weight 5% at manganese content, reduced slightly machinability.This is because owing to having reduced the solid solution capacity of nitrogen in austenitic stainless steel, so that steel becomes is unstable.And, should be appreciated that in the percentage by weight of manganese content exceedes 10% sample 28, deteriorated machinability, and further, also reduced slightly corrosion resistance.
Therefore, preferably, in austenitic stainless steel, the percentage by weight of the content of manganese is 5% or higher to 10% or lower.
Below specifically described based on this execution mode the present invention who is made by inventor of the present invention; But, the invention is not restricted to above-mentioned execution mode, and be transformable in the scope that does not depart from its spirit.
In will be understood that in all respects, now disclosed execution mode is exemplary and is not restrictive.Scope rather than foregoing description by claim represent scope of the present invention, and the institute that is intended to be included within implication and the scope being equal to the scope of claim changes.
The explanation of Reference numeral
1: superconducting wire
11: metal substrate (austenitic stainless steel)
12: force orientation intermediate layer
13:Y base superconducting layer
14: stabilizing layer
Claims (4)
1. for the substrate of the hts tape that uses in liquid nitrogen temperature or lower than the temperature of liquid nitrogen temperature,
Wherein, described substrate by contain percentage by weight be 0.4% or the austenitic stainless steel of higher nitrogen make,
Wherein, to contain percentage by weight be 20% or higher chromium to described austenitic stainless steel;
Wherein, to contain percentage by weight be 0.05% or lower carbon to described austenitic stainless steel;
Wherein, described austenitic stainless steel contain percentage by weight be 5% or higher manganese and percentage by weight be 10% or lower nickel.
2. a superconducting wire, it forms superconducting layer across intermediate layer on substrate, described substrate by comprise percentage by weight be 0.4% or the austenitic stainless steel of higher nitrogen make,
Wherein, to contain percentage by weight be 20% or higher chromium to described austenitic stainless steel;
Wherein, to contain percentage by weight be 0.05% or lower carbon to described austenitic stainless steel;
Wherein, described austenitic stainless steel contain percentage by weight be 5% or higher manganese and percentage by weight be 10% or lower nickel.
3. superconducting wire according to claim 2, wherein, described substrate is 1200MPa or higher in 0.2% yield stress of liquid nitrogen temperature.
4. a manufacture method for superconducting wire, the method comprises the following steps:
By contain percentage by weight be 0.4% or higher nitrogen and percentage by weight be 0.05% or the substrate made of the austenitic stainless steel of lower carbon on form intermediate layer, wherein, it is 20% or higher chromium that described substrate contains percentage by weight, percentage by weight be 5% or higher manganese and percentage by weight be 10% or lower nickel; And
On described intermediate layer, form superconducting layer,
Wherein, in forming the step in described intermediate layer and forming one of step of described superconducting layer, carry out the heat treatment of 700 ℃ to 950 ℃.
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| JP2009-223795 | 2009-09-29 | ||
| JP2009223795 | 2009-09-29 | ||
| PCT/JP2010/066757 WO2011040381A1 (en) | 2009-09-29 | 2010-09-28 | Substrate for superconducting wiring, superconducting wiring and production method for same |
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| CN102414764A CN102414764A (en) | 2012-04-11 |
| CN102414764B true CN102414764B (en) | 2014-06-04 |
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| US (1) | US20120021917A1 (en) |
| EP (1) | EP2485222A4 (en) |
| JP (1) | JPWO2011040381A1 (en) |
| CN (1) | CN102414764B (en) |
| WO (1) | WO2011040381A1 (en) |
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| JP5619731B2 (en) * | 2009-04-28 | 2014-11-05 | 公益財団法人国際超電導産業技術研究センター | Superconducting wire current terminal structure and superconducting cable having this current terminal structure |
| KR20140082634A (en) * | 2012-04-06 | 2014-07-02 | 후루카와 덴키 고교 가부시키가이샤 | Superconductor wire |
| JP6108888B2 (en) | 2013-03-13 | 2017-04-05 | 古河電気工業株式会社 | Peelable superconductor, method for manufacturing peelable superconductor, and method for repairing superconducting wire |
| US9634549B2 (en) | 2013-10-31 | 2017-04-25 | General Electric Company | Dual phase magnetic material component and method of forming |
| US10229776B2 (en) * | 2013-10-31 | 2019-03-12 | General Electric Company | Multi-phase magnetic component and method of forming |
| EP3231889B1 (en) * | 2016-03-23 | 2020-11-25 | General Electric Company | Method of forming multi-phase magnetic component |
| EP3282493B1 (en) * | 2016-08-10 | 2020-03-11 | Theva Dünnschichttechnik GmbH | High temperature superconductor tape having stainless steel substrate |
| DE102018133255A1 (en) * | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh & Co Kg | Super austenitic material |
| US11661646B2 (en) | 2021-04-21 | 2023-05-30 | General Electric Comapny | Dual phase magnetic material component and method of its formation |
| US11926880B2 (en) | 2021-04-21 | 2024-03-12 | General Electric Company | Fabrication method for a component having magnetic and non-magnetic dual phases |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101368252A (en) * | 2008-09-12 | 2009-02-18 | 江苏大学 | Non-nickel nitrogen austenite stainless steel |
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| JPS6013063A (en) * | 1983-07-05 | 1985-01-23 | Nippon Steel Corp | Structural austenitic stainless steel for very low temperature use |
| JPS6152351A (en) * | 1984-08-20 | 1986-03-15 | Nippon Steel Corp | Structural austenitic stainless steel having superior yield strength and toughness at very low temperature |
| DE3545182A1 (en) * | 1985-12-20 | 1987-06-25 | Krupp Gmbh | AUSTENITIC, NITROGEN CRNIMOMN STEEL, METHOD FOR THE PRODUCTION THEREOF AND ITS USE |
| US5102865A (en) * | 1988-10-31 | 1992-04-07 | General Atomics | Substrate for ceramic superconductor with improved barrier |
| US5086035A (en) * | 1990-02-06 | 1992-02-04 | Eastman Kodak Company | Electrically conductive article (i) |
| JPH05267888A (en) * | 1992-03-17 | 1993-10-15 | Ngk Insulators Ltd | Cylindrical superconducting magnetic shield |
| JP3546421B2 (en) * | 1995-03-31 | 2004-07-28 | 大同特殊鋼株式会社 | High-strength, high corrosion-resistant nitrogen-containing austenitic stainless steel |
| JPH11302798A (en) | 1998-04-20 | 1999-11-02 | Daido Steel Co Ltd | High nitrogen austenitic heat resistant steel |
| JP4316070B2 (en) * | 1999-10-07 | 2009-08-19 | 古河電気工業株式会社 | High strength oriented polycrystalline metal substrate and oxide superconducting wire |
| EP1122799A1 (en) | 2000-02-01 | 2001-08-08 | Zentrum für Funktionswerkstoffe, Gemeinnützige Gesellschaft mbH | Stainless steel substrate for superconducting films |
| US7129196B2 (en) * | 2003-07-21 | 2006-10-31 | Los Alamos National Security, Llc | Buffer layer for thin film structures |
| JP4887416B2 (en) * | 2009-11-27 | 2012-02-29 | 京楽産業．株式会社 | Decoration body unit, game board unit, and pachinko machine |
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- 2010-09-28 JP JP2011534237A patent/JPWO2011040381A1/en active Pending
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| CN101368252A (en) * | 2008-09-12 | 2009-02-18 | 江苏大学 | Non-nickel nitrogen austenite stainless steel |
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| JP2001－266666A 2001.09.28 |
| JP2011－110255A 2001.04.20 |
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| WO2011040381A1 (en) | 2011-04-07 |
| EP2485222A4 (en) | 2013-07-24 |
| CN102414764A (en) | 2012-04-11 |
| US20120021917A1 (en) | 2012-01-26 |
| EP2485222A1 (en) | 2012-08-08 |
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